JP2838148B2 - Silver halide photographic material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel indophenol dye and / or an indoaniline dye, and a silver halide photograph in which the yellowness of image silver is reduced by using the dye. It relates to a photosensitive material.

[0002]

2. Description of the Related Art Various dyes derived from phenol derivatives or naphthol derivatives are known as indophenol dyes or indoaniline dyes, and are useful as skeletons giving a blue tint. Further, the skeleton can be extended to a near-infrared region by modifying a substituent. However, in the conventional method, a large amount of dye had to be used to obtain a desired concentration because of a low molar extinction coefficient. Also, few of them have sufficient fastness to heat and light. Also, the covering power of silver halide emulsions is of great interest to emulsion manufacturers. This is because the use of an emulsion having a high covering power makes it possible to adjust the amount of silver required to maintain a constant optical density. However, the color tone of the developed silver of the emulsion grains giving the high covering power depends almost on the grain size and grain thickness, but gives a discomfort to the image observer due to the yellowish tint. The reason for the yellowish tint is that the developed silver also has a reduced size and thickness due to the phenomenon of the grain size and grain thickness, increases the blue light component scattering, and becomes light with a strong yellow tint. For this reason, Japanese Unexamined Patent Publication No.
As can be seen in JP-A Nos. 154251 and 61-285445, the use of a substantially water-insoluble dye to adjust the color tone and suppress the yellow tint has been performed. However, when a dye having a conventionally used structure is used, the dye has a side absorption at a light wavelength shorter than the main absorption, and this side absorption causes the image to take on a yellow tint. was there. Further, when a conventional dye is used by being added to the silver halide emulsion layer, there is a disadvantage that the sensitivity of the silver halide emulsion is lowered.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide photographic light-sensitive material in which the yellow color of an image is suppressed.

[0004]

Means for Solving the Problems The present inventors have found that the above problems can be solved by using an azomethine dye represented by the following general formula (I). General formula (I)

[0005]

Embedded image

In the formula, A is a dye residue obtained by removing one hydrogen atom from an indophenol or indoaniline dye,
L represents a divalent alkylene group, and Z represents a non-metallic atomic group having a 5- or 6-membered heterocyclic ring composed of a nitrogen atom and a carbon atom together with N. However, in the heterocycle, the carbonyl group is not directly bonded to N.

That is, the present invention relates to a silver halide photographic light-sensitive material having at least one silver halide photographic emulsion layer on at least one side of a support. The dye represented by the formula (I) in the silver halide emulsion layer and / or the other layer, the density of the unexposed area after the development processing due to the dye content. The object has been solved by a silver halide photographic light-sensitive material characterized in that the increase is 0.06 or less.

Hereinafter, the general formula (I) will be described in detail. A represents a dye residue obtained by removing one hydrogen atom from an indophenol or indoaniline dye, and preferred as indophenol or indoaniline dye represented by AH are the following general formulas (A-1) and (A −
2), (A-3), (A-4) or (A-5). General formula (A-1)

[0009]

Embedded image

In the formula, R ₁₁ represents an aryl group, R ₁₂ , R ₁₃ ,
R ₁₄ and R ₁₅ may be the same or different and each represents a hydrogen atom, an alkyl group, an aryl group, OR ₁₆ , NR ₁₆ R ₁₇ , N
R ₁₇ COR ₁₈ , NR ₁₇ SO ₂ R ₁₈ , SR ₁₈ , SO
₂ R ₁₈ , COOR ₁₆ , CONR ₁₆ R ₁₇ , SO ₂ NR ₁₆ R
₁₇ , NR ₁₇ COOR ₁₈ , a halogen atom, a cyano group, a nitro group, Q ₁₁ represents a hydroxyl group, NR ₁₆ R ₁₇ ,
R ₁₂ and R ₁₃ , R ₁₃ and Q _11, or R ₁₅ and Q ₁₁ may be respectively linked to form a 5- or 6-membered ring. Here R _16, R ₁₇ represents a group represented by hydrogen or R _18, R ₁₈ is an alkyl group, an aryl group or a heterocyclic group, R ₁₆ and R ₁₇ or R ₁₇ and R ₁₈ are each connected May form a 5- or 6-membered ring. General formula (A-2)

[0011]

Embedded image

In the formula, R ₂₁ is an alkyl group, an aryl group or a heterocyclic group, R ₂₆ is a halogen atom, OR ₂₇ , NR
₂₇ R ₂₈ , NR ₂₈ COR ₂₉ , and NR ₂₈ SO ₂ R ₂₉ , respectively, and R ₂₂ , R ₂₃ , R ₂₄ , R ₂₅ , and Q ₂₁ are respectively R ₁₂ , R ₁₃ , and R ₂₁ in the general formula (A-1). _14, the same meaning as R _15, Q _11. R ₂₇ , R ₂₈ and R ₂₉ are each represented by the general formula (A
It has the same meaning as R ₁₆ , R ₁₇ and R ₁₈ in -1). General formula (A-3)

[0013]

Embedded image

In the formula, R ₃₁ is a hydrogen atom, a halogen atom, O
R ₃₇ , NR ₃₇ R ₃₈ , NR ₃₈ COR ₃₉ , NR ₃₈ SO ₂ R ₃₉
R ₃₆ is a hydrogen atom, an alkyl group, OR ₃₇ , NR ₃₈ R ₃₉
R ₃₂ , R ₃₃ , R ₃₄ , R ₃₅ , and Q ₃₁ are respectively represented by R ₁₂ , R ₁₃ , R ₁₄ , and R in the general formula (A-1).
_15, Q ₁₁ as synonymous. R ₃₇ , R ₃₈ and R ₃₉ have the same meanings as R ₁₆ , R ₁₇ and R ₁₈ in formula (A-1), respectively. General formula (A-4)

[0015]

Embedded image

In the formula, L ₄₁ represents an alkylene group having 1 to 24 carbon atoms, a carbonylimino group having 1 to 24 carbon atoms or an imino group having 0 to 24 carbon atoms, and R ₄₂ , R ₄₃ , R ₄₄ ,
R ₄₅ and Q ₄₁ are each independently R ₁₂ ,
R _13, the same meaning as _{R 14, R 15, Q 11} . General formula (A-5)

[0017]

Embedded image

In the formula, R ₅₁ is a hydrogen atom, a halogen atom,
CONR ₅₆ R ₅₇ , SO ₂ NR ₅₆ R ₅₇ ,
R ₅₂ , R ₅₃ , R ₅₄ , R ₅₅ , and Q ₅₁ are respectively R ₁₂ , R ₁₃ , R ₁₄ , and R in the general formula (A-1).
_{15, Q 11} as synonymous. R ₅₆ and R ₅₇ have the same meanings as R ₁₆ and R ₁₇ in formula (A-1), respectively.

[0019]

In the formula, R ₆₁ is a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, NR ₆₇ COR ₆₈ , NR ₆₇ SO
_{2 represents} R ₆₈ , NR ₆₆ CONR ₆₆ R ₆₇ , and NR ₆₇ COOR ₆₈ , and R ₆₂ , R ₆₃ , R ₆₄ , R ₆₅ , and Q ₆₁ represent R ₁₂ , R ₁₃ , and R _{14 in the} general formula (A-1), respectively. , R ₁₅ and Q ₁₁ have the same meanings. R ₆₆ , R ₆₇ and R ₆₈ are each represented by the general formula (A-
It has the same meaning as R ₁₆ , R ₁₇ and R ₁₈ in 1).

The above general formulas (A-1), (A-2) and (A
In the description of each group of -3), (A-4) and (A-5), examples of the halogen atom include F, Cl, Br and I. The alkyl group may have 1 to 30 carbon atoms.
(E.g., methyl, ethyl, n-propyl, n-octyl, n-butyl, t-butyl, isooctyl, n-dodecyl, isostearyl, n-hexyl,
Isopropyl, t-amyl) is preferable, and a substituent (for example, F, Cl, Br, OH, COOH, CN, an ester group, an amino group, a carbonamide group, an acyl group, an aryl group, a sulfonamide group, an alkoxy group, or an alkyl group) Or an arylsulfonyl group, a carbamoyl group, a sulfamoyl group, a ureido group). The aryl group is preferably an aryl group having 6 to 10 carbon atoms (for example, phenyl or naphthyl), and has a substituent (for example, an alkyl group or a group mentioned as a substituent which the alkyl group may have). May be. 5 or 6 as the heterocyclic group
Membered heterocycles (eg, imidazole, pyrazole, oxazole, isoxazole, pyridine, 1,2,4-
Triazole, 1,2,3,4-tetrazole, thiazole, benzoxazole, benzimidazole, benzothiazole, furan, tetrahydrofuran, thiophene, pyrrole, pyrrolidine, piperidine, morpholine,
A ring such as indole) may preferably have a substituent (for example, an alkyl group or a group mentioned as a substituent which the alkyl group may have).

In the general formulas (A-1) to (A-5),
Preferred are those represented by the general formula (A-1) or (A-2). The divalent linking group represented by L is preferably an alkylene group having 1 to 24 carbon atoms, more preferably 1 to 3 carbon atoms.
Alkylene group (e.g., methylene, ethylene, propylene) and a substituent (e.g., methyl, ethyl, isopropyl, n-butyl, n-hexyl, n-dodecyl,
n-hexadecyl, an alkyl group having 1 to 18 carbon atoms such as isooctyl, a phenyl group, a benzyl group, a phenethyl group,
Ester groups such as ethoxycarbonyl and n-dodecyloxycarbonyl). Specific examples include the following. Specific examples of L

[0023]

Embedded image

[0024]

Embedded image

The non-metallic atomic group having a 5- or 6-membered heterocyclic group together with N represented by Z may be a single ring or a condensed ring, for example, 1-pyrazolyl, 1-imidazolyl,
1,2,4-triazol-1-yl, 1,2,3,4
-Tetrazol-1-yl, benzotriazol-1-
Yl and 1,2,3,4-tetrazol-2-yl are preferable, and a substituent (for example, an alkyl group such as methyl, ethyl or n-propyl, a phenyl group, a 4-chlorophenyl group,
3,5-dichlorophenyl group, benzyl group, 1 or 2-
Naphthyl group, methoxy, carbonyl, ester group such as n-hexyloxycarbonyl). Specific examples include the following.

[0026]

Embedded image

[0027]

Embedded image

[0028]

Embedded image

[0029]

Embedded image

Specific examples of the dye represented by formula (I) are shown below, but the present invention is not limited thereto.

[0031]

Embedded image

[0032]

Embedded image

[0033]

Embedded image

[0034]

Embedded image

[0035]

Embedded image

[0036]

Embedded image

The dye represented by formula (I) is disclosed in
Nos. -103477, 3-79672 and 2-129
No. 268 or the following method.

Synthesis Example 1 Synthesis of Exemplified Compound I-5 2- {3 ″-(p-cyanophenyl) ureido} -5- {α- (2 ′-(5′-phenyl) ) Tetrazolyl) tetradecanoylaminophenol (623 mg) in ethyl acetate-methanol (1: 1, 4).
0 ml) solution of sodium carbonate (530 mg) in water (10 ml), 4- (N-ethyl-N-
A solution of methanesulfonamidoethylamino) -2-methylaniline 3/2 sulfate monohydrate (480 mg) in water (10 ml) and ammonium persulfate (684 ml)
Add the solution of g) in water (10 ml) and stir for 30 minutes. Add water and extract twice with ethyl acetate. The organic layer was collected, the solvent was distilled off under reduced pressure, and column chromatography (developing solvent, methylene chloride: methanol = 20:
When purified in 1), Exemplified Compound I-5 (645 mg, 73
%)was gotten. λmax = 616 nm, ε = 2.85 × 10 ⁴ (ethyl acetate)

Synthesis Example 2 Synthesis of Exemplified Compound I-6 2- {3 ″-(p-cyanophenyl) ureido} -5
{Α- (2 ′-(5′-β′-naphthyl) tetrazolyl)} tetradecanoylaminophenol (673 m
g), sodium carbonate (530 mg), 4- (N-ethyl-N-methanesulfonamidoethylamino) -2-methylaniline 3/2 sulfate monohydrate (480 mg) and ammonium persulfate (684 mg). Exemplified compound I-6 (780 mg, 83%) in the same manner as in the method in Example 1.
was gotten. λmax = 617 nm, ε = 2.61 × 10 ⁴ (ethyl acetate)

Synthesis Example 3 Synthesis of Exemplified Compound I-7 2- {3 ″-(p-cyanophenyl) ureido} -5
{Α- (2 ′-(5′-benzyl) tetrazolyl)} tetradecanoylaminophenol (637 mg), sodium carbonate (530 mg), 4- (N-ethyl-N-methanesulfonamidoethylamino) -2-methyl Aniline 3
Example compound I-7 (714 mg, 79%) was obtained from // 2 sulfate monohydrate (480 mg) and ammonium persulfate (684 mg) in the same manner as in the method of Synthesis Example 1. λmax = 620 nm, ε = 2.73 × 10 ⁴ (ethyl acetate)

Synthesis Example 4 Synthesis of Exemplified Compound I-2 2- {3 ″-(p-cyanophenyl) ureide} -5-
{Α- (2 ′-(5′-β′-naphthyl) tetrazolyl)} tetradecanoylaminophenol (673 m
g), p-diethylaminoaniline sulfate (315 m
g), methanol (15 ml), triethylamine (37
8 mg) in a solution of N-bromosuccinimide (223 m 2).
g), and a solution of acetone (4 ml) is added and stirred for 30 minutes. The precipitated crystals were collected by filtration and washed with methanol to obtain crude crystals (450 mg). Crude crystals (450mg)
Was recrystallized from a mixed solvent of methanol and chloroform (20 ml, methanol: chloroform = 1: 1) to obtain Exemplified Compound I-2 (440 mg, 53%). λmax = 600 nm, ε = 2.83 × 10 ⁴ (ethyl acetate)

The dye used in the present invention can be dispersed in an emulsion layer or other hydrophilic colloid layers (intermediate layer, protective layer, antihalation layer, filter layer, etc.) by various known methods. A method in which the dye of the present invention is directly dissolved or dispersed in an emulsion layer or a hydrophilic colloid layer, or a method in which the dye is dissolved or dispersed in an aqueous solution or a solvent and then used in the emulsion layer or the hydrophilic colloid layer. Suitable solvents, for example, methyl alcohol, ethyl alcohol, propyl alcohol, methyl cellosolve, JP-A-48-9715, U.S. Pat.
No. 6,830, it can be added to the emulsion in the form of a solution dissolved in a halogenated alcohol, acetone, water, pyridine or the like, or a mixed solvent thereof. A method in which a compound obtained by dissolving a compound in an oil, that is, a solvent substantially insoluble in water and having a boiling point of about 160 ° C. or higher is added to a hydrophilic colloid solution and dispersed. Examples of the high boiling point solvent include alkyl phthalates (such as dibutyl phthalate and dioctyl phthalate) and phosphates (such as diphenyl phosphate and triphenyl phosphate) as described in US Pat. No. 2,322,027. , Tricresyl phosphate, dioctyl butyl phosphate), citrate esters (eg, tributyl acetyl citrate), benzoate esters (eg, octyl benzoate), alkylamides (eg, diethyl laurylamide), fatty acid esters (eg, dibutoxy) Ethyl succinate, diethyl azelate) and trimesates (eg, tributyl trimesate) can be used. In addition, the boiling point is about 30 ° C to about 150 ° C.
Organic solvents, for example, ethyl acetate, lower alkyl acetates such as butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate or a solvent easily soluble in water, for example, methanol or Alcohol such as ethanol can also be used.

Here, the use ratio of the dye to the high boiling point solvent is preferably 10 to 1/10 (weight ratio). A method of incorporating the dye and other additives of the present invention as a polymer latex composition filled with a photographic emulsion layer or other hydrophilic colloid layer. Examples of the polymer latex include a polyurethane polymer and a polymer polymerized from a vinyl monomer [a suitable vinyl monomer is an acrylate (methyl acrylate, ethyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate,
Dodecyl acrylate, glycidyl acrylate, etc.),
α-substituted acrylate (methyl methacrylate,
Butyl methacrylate, octyl methacrylate, glycidyl methacrylate, etc.), acrylamide (butyl acrylamide, hexyl acrylamide, etc.), α-substituted acrylamide (butyl methacrylamide, dibutyl methacrylamide, etc.), vinyl ester (vinyl acetate, vinyl butyrate, etc.), vinyl halide (Vinyl chloride, etc.), vinylidene halide (vinylidene chloride, etc.), vinyl ether (vinyl methyl ether, vinyl octyl ether, etc.), styrene, X-substituted styrene (α-methyl styrene, etc.), the substituted styrene (hydroxystyrene, chlorostyrene) , Methylstyrene, etc.), ethylene, propylene, butylene, butadiene, acrylonitrile and the like. These may be used alone or in combination of two or more, or other vinyl monomers may be mixed as a minor component. Other vinyl monomers include itaconic acid acrylic acid, methacrylic acid, hydroxyalkyl acrylate, hydroxyalkyl methacrylate, sulfoalkyl acrylate, sulfoalkyl methacrylate, styrene sulfonic acid, and the like. ] Etc. can be used.

These filled polymer latexes are described in JP-B-51-39853, JP-A-51-59943, and
No. 3-137131, No. 54-32552, No. 54-
No. 107941, No. 55-133465, No. 56-1
No. 9043, No. 56-19047, No. 56-1268
No. 30, 58-149038. Here, the use ratio of the dye to the polymer latex is preferably 10 to 1/10 (weight ratio).

A method in which a compound is dissolved using a surfactant. Useful surfactants may be oligomers or polymers. The details of this polymer are described in JP-A-53-138726, JP-A-60-200251, JP-A-60-203935 and Japanese Patent Application No. 59-12766. A method in which a hydrophilic polymer is used in place of the high boiling point solvent described above or in combination with the high boiling point solvent. Regarding this method, for example, US Pat. No. 3,619,195, West German Patent 1,
957,467. A microcapsule method using a polymer having a carboxyl group, a sulfonic acid group or the like in a side chain as described in JP-A-59-113434. In addition, for example, a hydrosol of a lipophilic polymer described in JP-B-51-39835 may be added to the hydrophilic colloid dispersion obtained above.

As the hydrophilic colloid, gelatin is a typical one, but any other conventionally known colloids usable for photography can be used. In the present invention, the dye-containing layer is an emulsion layer, a protective layer, a back layer, an antihalation layer, and an intermediate layer, and may be added separately. Preferred containing layers are an emulsion layer and a back layer. In the present invention, the content of the dye is preferably from 0.06 to 0.01, more preferably from 0.03 to 0.01, as a concentration increase by the addition of the dye. Here, when the transmission density exceeds 0.06, the apparent fog density is increased, and the appearance is poor, and the silver tone is strongly affected by the color tone adjusting agent, so that a desired silver tone cannot be obtained. Conversely 0.01
Below, the degree of color tone improvement is inferior. The optimum amount of the dye to be added depends on the concentration of the support, the extinction coefficient of the dye, the maximum absorption wavelength of the dye, and the color tone of the developed silver, but is from 1 × 10 ^-7 mol / m ² to 1 × 10 ^-4 mol / m ^2. It is preferable to use It is more preferably from 2 × 10 ⁻⁷ mol / m ² to 2 × 10 ⁻⁵ mol / m ² , and most preferably from 5 × 10 ⁻⁷ mol / m ² to 1.5 × 10 5 mol / m ^2.
10 ⁻⁵ mol / m ² .

The covering power referred to in the present invention is a value obtained by dividing the transmission density of a uniformly blackened photosensitive material by the developed silver amount (mg / dm ² ) at that portion and multiplying by 10,000. The covering power of silver halide emulsions is of great interest to emulsion manufacturers. This is because the use of an emulsion having a high covering power can save the amount of silver required to maintain a constant transmission density. The covering power in the present invention is 60 or more, preferably 70
That is all.

The emulsion grains used in the present invention are preferably tabular grains. As the tabular photosensitive silver halide emulsion used in the present invention, silver chloride, silver chlorobromide, silver bromide, silver iodobromide, and silver chloroiodobromide can be used. Silver halide or silver iodobromide is preferred,
In particular, the iodine content is preferably from 0 mol% to 3.5 mol%. The projected area diameter of the tabular emulsion of the present invention is 0.3 to 2.0 μm.
m, particularly preferably 0.5 to 1.5 μm. The distance between parallel planes (particle thickness) is 0.05 μm.
To 0.5 μm, particularly preferably 0.1 to 0.25 μm. The tabular silver halide grains can be produced by appropriately combining methods known in the art.
Tabular silver halide emulsions are disclosed in JP-A-58-12792.
1, JP-A-58-113,927, JP-A-58-11
It can be easily prepared by referring to the method described in U.S. Pat. Also, pBr 1.
In an atmosphere having a relatively low pBr value of 3 or less, tabular grains form seed crystals in which 40% or more exist by weight, and the seed crystals are grown while simultaneously adding silver and a halogen solution while maintaining the same pBr. To be obtained. It is desirable to add a silver and halogen solution so that no new crystal nuclei are generated during the grain growth process.

The size of the tabular silver halide grains is determined by selecting the type and amount of the temperature controlling solvent, the silver salt used during grain growth,
And the rate of addition of the halide can be controlled. Further, among the tabular silver halide grains, monodisperse hexagonal tabular grains are particularly useful grains. The details of the structure and production method of the monodisperse hexagonal tabular grains used in the present invention are described in JP-A-63-151618.
For the present invention, so-called halogen conversion type (conversion type) particles as described in British Patent 635,841 and US Pat. No. 3,622,318 can be used particularly effectively. The degree of halogen conversion is from 0.2 mol% to 2 mol%, especially from 0.2 mol% to 0.4 mol, based on the amount of silver.
l% is good. In silver iodobromide, grains having a structure having a high iodine layer inside and / or on the surface are particularly preferable. By converting the surface of the tabular silver halide grains of the present invention, a silver halide emulsion with higher sensitivity can be obtained.

As a halogen conversion method, usually, an aqueous halogen solution having a smaller solubility product with silver than the halogen composition on the grain surface before the halogen conversion is added. For example, a potassium bromide and / or potassium iodide aqueous solution is added to silver chloride or silver chlorobromide tabular grains, and a potassium iodide aqueous solution is added to silver bromide or silver iodobromide tabular grains. To convert.
The concentration of the aqueous solution to be added is preferably light, preferably 30% or less, more preferably 10% or less. In addition, 1 minute per mole of silver halide before halogen conversion
It is preferred to add the conversion halogen solution at a rate of less than or equal to mol%. Further, at the time of halogen conversion, a part or all of the sensitizing dye and / or the silver halide-adsorbing substance of the present invention may be present, and instead of the converted halogen aqueous solution, silver bromide or silver iodobromide may be used. And fine silver halide grains of silver iodide. The size of these particles is
0.2 μm or less, preferably 0.1 μm or less, particularly 0.0
It is desirable that the thickness be 5 μm or less. The halogen conversion method of the present invention is not limited to any one of the above methods, but may be used in combination according to the purpose. The silver halide composition on the grain surface before halogen conversion is preferably 3% by mole or less in iodine content.
In particular, it is preferably at most 1.0 mol%. In carrying out the halogen conversion by the above method, a method in which a silver halide solvent is present is particularly effective. Preferred solvents include thioether compounds, thiocyanates, and tetrasubstituted thioureas. Among them, thioether compounds and thiocyanates are particularly effective, and it is preferable to use 0.5 g to 5 g of thiocyanate and 0.2 g to 3 g of thioether per 1 mol of silver halide.

In the present invention, the tabular silver halide emulsion may be a mixture of two or more kinds of silver halide emulsions. The grain size, halogen composition, sensitivity, etc. of the emulsions to be mixed may be different. For example, a spherical or potato-shaped photosensitive emulsion or a photosensitive silver halide emulsion composed of tabular grains having a grain size of three times or more the grain thickness may be used in the same layer or in different layers as described in JP-A-58-127921. It may be used for a layer. When used in different layers, the light-sensitive silver halide emulsion composed of tabular grains may be on the side closer to the support or, conversely, on the side farther away. Cadmium salt, zinc salt, lead salt, thallium salt, iridium salt or its complex salt, rhodium salt or its complex salt, iron salt or iron complex salt coexist in the process of silver halide grain formation or physical ripening during silver halide production May be.
During grain formation, a so-called silver halide solvent such as a thiocyanate, a thioether compound, a thiazolidineethion, or a tetrasubstituted thiourea may be used. Among them, thiocyanate, tetrasubstituted thiourea and thioether are preferred solvents in the present invention.

There are no particular restrictions on the emulsion sensitization method and various additives used in the light-sensitive material of the present invention.
Japanese Patent No. 68539 can be used. Item The location 1 Chemical sensitization method From page 13, line 13, upper right column to line 16, lower left column, JP-A-2-68539. 2 Antifoggants / stabilizers: From page 10, lower left column, line 17 to page 11, upper left column, line 7; and from page 3, lower left column, line 2 to page 4, lower left column. 3 Spectral sensitizing dyes, page 4, lower right column, line 4 to page 8, right lower column 4 Surfactants and antistatic agents Page 11, page 11, upper left column, line 14 to page 12, upper left column, line 9 5 Matting agent / slip agent / plasticizer Page 12, 12th line, upper left column to 10th line, upper right column. From page 10, lower left column, line 10 to lower right column, line 1 6 Hydrophilic colloid From page 12, upper right column, line 11 to line 16, lower left column. 7 Hardener From page 12, lower left column, line 17 to page 13, upper right column, line 6; 8 Support: 13th page, upper right column, lines 7 to 20. 9 Dyes and mordants From page 13, lower left column, line 1 to page 14, lower left column, line 9. 10 Developing method JP-A-2-103037, page 16, upper right column, line 7 to page 19, lower left column, line 15; From page 3, lower right column, line 5 to page 6, upper right column, line 10 of JP-A-2-15837.

[0053]

Next, the present invention will be described in detail with reference to examples. Example 1 Preparation of Support A Corona discharge treatment was carried out on a biaxially stretched blue dyed polyethylene terephthalate film ^(*) having a thickness of 175 μm, and both sides were coated with a wire bar coater so that the following coating amount was obtained. Dried at ℃ for 1 minute. · Butadiene - styrene copolymer latex butadiene / styrene weight ratio ^{= 31/69 0.32g / m 2} · 2,4- dichloro-6-hydroxy -s- triazine sodium salt 4.2mg / m ² (*) Polyethylene Terephthalate films contain 1.4-bis (2,6-diethylanilino) anthraquinone. Next, both sides were coated with a wire bar coater so as to have the following coating amount, and dried at 150 ° C. for 1 minute.・ Gelatin 80mg / m ²・ Dye A (solid dispersion) 16mg / m ²

[0054]

Embedded image

Preparation of Dye A Solid Dispersion Water (434 ml) and Triton X-200 surfactant (T
A 6.7% solution of X-200) (53 g) (sold by Rohm & Haas) was placed in a 1.5 liter screw cap bottle. 20 g of the dye and zirconium chloride (Zr
O) beads (800 ml) (2 mm diameter) were added, the bottle was tightly capped, placed in a mill and the contents milled for 4 days. The contents were dissolved in a 12.5% aqueous gelatin solution (1
60 g) and placed on a roll mill for 10 minutes to reduce foam. The resulting mixture was filtered to remove ZrO beads. If left as is, particles having a particle size of 3 μm or more are contained, which is not preferable. Therefore, 50 μm particles of 1 μm or more
It was removed by centrifuging at 00 rpm for 5 min. Preparation of Dye Emulsion Dispersion As shown in Table 1, a comparative dye or an exemplified dye was emulsified and dispersed by the following dispersion method. 300 mg of the dye was dissolved in 40 cc of N, N-dimethylformamide to obtain solution I. 11 g of gelatin and 0.5 g of emulsifying dispersant A were dissolved in 120 cc of water to prepare a solution II. Solution I was added to Solution II for 20 seconds while stirring at high speed with a homogenizer, emulsified and dispersed, and then 2-phenoxyethanol was added for 5 minutes.
10 mg of 0 mg proxel was added to obtain a dye emulsion dispersion.

[0056]

Embedded image

[0057]

Embedded image

Preparation of Emulsion A 4.5 g of potassium bromide and 20.6 gelatin in 1 liter of water
g, thioether HO (CH ₂ ) ₂ S (CH ₂ ) ₂ S
_2.5 cc of a 5% aqueous solution of (CH ₂ ) ₂ OH was added, and 6
3.43 g of silver nitrate was stirred into the solution maintained at 5 ° C.
Aqueous solution of 2.97 g of potassium bromide, 0.363 of potassium iodide
g of the aqueous solution was added by the double jet method in 37 seconds. Subsequently, after adding 0.9 g of potassium bromide, an aqueous solution containing 4.92 g of silver nitrate was added over 13 minutes. Thereafter, the temperature was raised to 70 ° C., and a 25% ammonia solution 18c
After the addition of c, neutralization was performed by adding 17 cc of 100% acetic acid. Subsequently, an aqueous solution of 133.49 g of silver nitrate and an aqueous solution of potassium bromide were added in 35 minutes by a control double jet method while maintaining the potential at pAg 8.2. did. At this time, the flow rate at the end of the addition is 2.
Accelerated to 6 times. After completion of the addition, 15 cc of a 2N potassium thiocyanate solution was added, and 38.5 cc of a 1% potassium iodide aqueous solution was added over 30 seconds. Thereafter, the temperature was lowered to 35 ° C., and after removing soluble salts by a sedimentation method, the temperature was raised to 40 ° C., 68 g of gelatin and 2.35 g of phenoxyethanol were added, and potassium bromide was added.
The pAg was adjusted to 8.20. The prepared silver halide grains are tabular and have an average projected area circle equivalent diameter of 1.4 μm.
m, and the average particle thickness was 0.20 μm. Next, the temperature of the emulsion was raised to 56 ° C., the pH was adjusted to 5.9, and 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene and sensitizing dye 1 were added. After another 10 minutes, sodium thiosulfate, potassium thiocyanate, and chloroauric acid were added to perform chemical sensitization to obtain Emulsion A.

[0059]

Embedded image

Preparation of Emulsion Coating Solution The following chemicals were added to Emulsion A per mole of silver halide to prepare a coating solution.・ Dye emulsion Table 1 ・ Polymer latex (poly (ethyl acrylate / methacrylic acid) = 97/3) 20.0 g ・ Hardener 1,2-bis (vinylsulfonylacetamide) ethane 2.4 g ・ 2,6- Bis (hydroxyamino) -4-diethylamine-1,3,2-triazine 76 mg ・ Sodium polyacrylate (average molecular weight 41,000) 2.1 g ・ Sodium polystyrene sulfonate (average molecular weight 600,000) 1.0 g ・ Dextran (Molecular weight 39,000) 23.6 g-Trimethylolpropane 9.8 g-Potassium hydroquinone monosulfonate 9.7 g

[0061]

Embedded image

Preparation of Photographic Material The amount of silver applied on both sides of the support A at the same time as the surface protective layer solution was 2 g / m ² per side. The surface protective layer was prepared so that each component had the following coating amount, and samples 1 to 12 were obtained. Content of surface protective layer Coating amount ・ Gelatin 1.138 g / m ²・ Dextran (average molecular weight 39,000) 0.228 g / m ²・ 4-hydroxy-6-methyl-1,3,3a, 7-tetrazain Den 0.0155 g / m ² · sodium polyacrylate (average molecular weight 41,000) 0.023 g / m ²

[0063]

Embedded image

[0064] Polymethyl methacrylate (average particle size 3.7μm) 0.088g / m ² · Proxel 0.0006 g / m ²

Evaluation of Performance Evaluation of Sensitivity Photographic material 1-12 with green light having a peak at 550 nm
A 1/10 second exposure was given from both sides through a wedge-shaped wedge. Next, an automatic processor FPM-
Using 9000, developing solution RD7, and fixing solution Fuji F, dry-dry processing was performed for 45 seconds. At that time, the developer temperature was 35 ° C., the fixer temperature was 30 ° C., and the fixer temperature was 20 ° C.
I went in. The density was measured with respect to the exposure, and the sensitivity was determined. Density increase value D due to addition of dye An unexposed sample was processed by the above-mentioned developing machine, and the difference between the obtained green density value and the green density value of the sample to which no dye was added was determined. Evaluation of Covering Power Covering power is D under the above-mentioned exposure and development conditions.
The amount of silver in the max part was measured by the X-ray fluorescence method, and the value obtained by dividing the density by the amount of developed silver (mg / dm ² ) was determined by multiplying by 10,000. Evaluation of Developed Silver Tone Developed silver tone, transmission, blackening density, under the above development conditions,
The color tone of the sample was observed using a sample uniformly exposed over a relatively large area so as to be 1.0. Evaluation of outer folding knick desensitization Before the exposure and the development, the coated sample was heated at 25 ° C and 60 ° C.
After adjusting the humidity at% RH for 2 hours, the sample was pressed against a stainless steel rod having a diameter of 5 mm and folded at an angle of 30 degrees for 10 seconds. After the above-mentioned exposure and development, the sensitivity of the sample in which the emulsion surface on the bending rod side was removed and the sensitivity of the sample in which the exposure and development were carried out without performing such bending, and the emulsion surface was unilaterally removed, were performed. The sensitivity difference was determined. Sensitivity difference is fog +0.1
The difference in the logarithmic value of the exposure amount giving the density value of was calculated.

[0066]

[Table 1]

[0067]

[Table 2]

Example 2 Contents of Back Dye Dye Emulsion Table 3 Gelatin 3.4 g / m ²

[0069]

Embedded image

Sodium polystyrene sulfonate (average molecular weight: 600,000) 15 mg / m ² 1,2, bis (vinylsulfonylacetamide) ethane 68 mg / m ² Colloidal silica 0.4 g / m ² Polymer latex (poly (ethyl acrylate / methacrylic) acid) = 97/3) 2g / m 2 back surface protective layer of the contents of gelatin 0.57 g / m ² polymethyl methacrylate (average particle size 3.7μm) 0.09g / m ²

[0071]

Embedded image

Preparation of Photographic Material The back dye coating solution was coated simultaneously with the surface protective layer on one side of a blue-colored 175 μm polyethylene terephthalate transparent support to form a back. Next, an emulsion coating solution was prepared using the same emulsion A as in Example 1 and using the same formulation as in Example 1. However, the dye emulsion in Example 1 was not added. Next, this emulsion coating solution together with the surface protective layer of Example 1 was coated on the opposite side of the above-mentioned back surface with a coating silver amount of 4 g / g.
to obtain a coated samples 13 to 22 so as to m ^2. Evaluation of Coated Sample In the same manner as in Example 1, the sensitivity, ΔDv, covering power, and developed silver tone were observed. However, single-sided exposure was used.

[0073]

[Table 3]

As is evident from Table 1, the use of the dye of the present invention reduces the yellowing of the developed silver tone and has an effect of improving the tone. In addition, the outer folding desensitization is reduced. On the other hand, in the comparative example, when the dye is added until the yellowing of the developed silver tone is reduced, the outer fold desensitization worsens, while the amount of the dye added is reduced so that the outer fold desensitization does not occur. Then, it is clear that the developed silver tone becomes yellowish. Further, as can be seen from Example 2 and Table 2, even when the dye of the present invention is added to the back, the effect of improving the developed silver tone is apparent.

[0075]

By using the dye represented by the general formula (I) for a light-sensitive material having a silver halide emulsion layer having a covering power of 60 or more, it is possible to suppress the color tone of a developed silver image from becoming yellowish. In addition, a light-sensitive material having less desensitization due to outer folding was obtained.

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int.Cl. ⁶ , DB name) G03C 1/35

Claims (1)

(57) [Claims] Claims 1. At least one side of a support has a small
Halogen having at least one silver halide photographic emulsion layer
Coating of the silver halide emulsion layer in a silver halide photographic material
A force of 60 or more, and the silver halide emulsion layer and / or
Or in another layer, a dye represented by the following general formula (I).
Of the dyestuff in the unexposed area transmission density after development
Characterized in that it is included so that the density increase is 0.06 or less.
Silver halide photographic light-sensitive material. General formula (I) In the formula, A represents a dye residue obtained by removing one hydrogen atom from an indophenol or indo-allinine dye, and L represents an alkylene dye.
Of constituting the emission group, Z is a nitrogen atom and a carbon atom with N
A non-metallic atomic group having a 5- or 6-membered heterocyclic ring , respectively. However, in the heterocycle, the carbonyl group is not directly bonded to N.